JPH0820560A - Production of ester compound - Google Patents

Abstract

PURPOSE:To obtain an ester compound without producing hydrogen fluoride as a byproduct by reacting a compound having an acyl fluoride group with a specific silane compound. CONSTITUTION:A compound expressed by the formula Rf<1>(CO)F or the formula F(CO)Rf<2>(CO)F (Rf<1> is a perfluoroalkyl or a perfluoroalkyl ether; Rf<2> is a perfluoroalkylene or a perfluoroalkylene ether) which has at least one acyl fluoride group in the molecule is reacted with a silane compound expressed by the formula R<1>nSi(OR<2>)4-n which has at least one silicon-carbon bonding through an oxygen atom in the molecule at 20-80 deg.C. Since hydrogen fluoride is not formed as a byproduct during a manufacturing process, the process is excellent in safety and workability and free from fear of corrosion of an apparatus.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an ester compound, and more particularly to a method for producing an ester compound from a compound having an acylfluoride group without causing byproduct of hydrogen fluoride.

[0002]

2. Description of the Related Art Conventionally, when synthesizing an ester compound from a compound having an acylfluoride group, an organic compound having a hydroxyl group has been reacted. While this reaction is an efficient reaction that proceeds almost quantitatively, hydrogen fluoride is generated as a by-product, so that it is not possible to use glassware or a glass-lined container during the reaction. there were. In addition, since hydrogen fluoride is an extremely toxic substance that penetrates into the body from the skin or the like and invades the bone, it has a drawback of poor workability.

[0003]

The inventors of the present invention have diligently studied a method of synthesizing an ester compound from a compound having an acylfluoride group without producing hydrogen fluoride as a by-product, and as a result, the conventional method has been used. The present inventors have found that the purpose can be easily achieved by using a special silane compound instead of the above-mentioned organic compound having a hydroxyl group, and arrived at the present invention. Therefore, the object of the present invention is
It is an object of the present invention to provide a method for synthesizing an ester compound from a compound having an acyl fluoride group without producing hydrogen fluoride as a by-product.

[0004]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
A compound having at least one acylfluoride group in the molecule and at least one bond between the silicon atom and the carbon atom through the oxygen atom (that is, ≡Si—O—C≡ bond) exist in the molecule. It was achieved by a method for producing an ester compound, which comprises reacting with a silane compound.

The reaction mechanism of the present invention is represented by the following chemical formula 1.

Embedded image Thus, in the reaction of the present invention, hydrogen fluoride is not produced at all, but a fluorosilane compound is produced instead.

Fluorosilane compounds are relatively stable compounds. For example, the boiling point of trimethylfluorosilane in which the other three substituents bonded to the silicon atom are methyl groups is about 17 ° C. under atmospheric pressure, Easy to separate and remove. Further, the reaction of the present invention may be carried out at room temperature or higher, for example, 20 to 80 ° C., but particularly 40 to 70 ° C.
It is preferable to react within the range.

As the compound having an acyl fluoride group in the molecule of the present invention, those represented by the following chemical formula 2 are preferably used, but the compounds are not limited thereto.

Embedded image However, Rf ¹ in the above formula is a monovalent perfluoroalkyl group, or a perfluoroalkyl ether group having at least one ether-bonded oxygen atom, and Rf ² is a divalent perfluoroalkylene group, or at least A perfluoroalkylene ether group having one ether-bonded oxygen atom.

Examples of Rf ¹ and Rf ² are represented by the following chemical formula 3.

Embedded image However, 1 (el) in the above formula is an integer of 1 to 50, and m is 1
To an integer of 20 and n is an integer of 1 to 10, p and q
Are integers of p ≧ 1, q ≧ 1, 2 ≦ p + q ≦ 50, respectively.

Next, typical examples of the compound used in the present invention having at least one acylfluoride group in the molecule will be shown, but the present invention is not limited thereto. CH ₃ COF, CF ₃ COF, C ₃ F ₇ CO
F, FOC (CF ₂ ) ₃ COF, FOCCF ₂ O (CF
₂ ) ₃ COF, FOCCF ₂ O (C ₂ F ₄ O) ₁₆ (CF
₂ O) ₈ CF ₂ COF and compounds represented by the following chemical formulas 4 to 6.

[0010]

[Chemical 4]

Embedded image

[0011]

[Chemical 6] However, l (el) in the above formula is an integer of 1 to 50, m + n
Is an integer of 2 to 50, p is an integer of 1 to 20, and q is 1
It is an integer of 10.

In the present invention, a silane compound having at least one bond between a silicon atom and a carbon atom (that is, ≡Si—O—C≡ bond) through an oxygen atom in the molecule is represented by the general formula R ¹
It is an organosilane compound represented by _n Si (OR ² ) _4-n . However, R ¹ and R ² in the general formula are hydrogen atoms or unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and n is an integer of 0 to 3.

Specifically, it is an organosilane compound represented by the following chemical formulas 7 to 10.

[Chemical 7]

Embedded image

[Chemical 9]

[Chemical 10]

In the above Chemical Formulas 7 to 10, R ^{3 to} R ⁵ are the same as R ¹ in the above general formula, and are a hydrogen atom or the same or different unsubstituted or substituted monovalent hydrocarbon group. R ^{6 to} R ⁹ are the same as R ² in the above general formula, are the same or different unsubstituted or substituted monovalent hydrocarbon groups, and include a hetero atom such as a nitrogen atom or an oxygen atom in the middle of the bond. You may stay.

Examples of the unsubstituted or substituted monovalent hydrocarbon group for R ¹ , R ² or R ^{3 to} R ⁹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group and ter-butyl group. Group, alkyl group such as hexyl group, octyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group; vinyl group, allyl group,
Alkenyl groups such as propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group, cyclohexenyl group; alkynyl groups such as ethynyl group, propynyl group, butynyl group, methylpropynyl group, dimethylpropynyl group;

An aryl group such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group; an aralkyl group such as a benzyl group and a phenylethyl group; and at least a part of hydrogen atoms of these groups is a halogen atom, a cyano group or the like. Substituted groups such as 3,3,3-trifluoropropyl group, 6,6
6,5,5,4,4,3,3-nonafluorohexyl group, heptadecafluorodecyl group, chloromethyl group, 2
Examples thereof include groups having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, such as -chloroethyl group, 3-chloropropyl group, and cyanoethyl group.

Specific examples of the silane compound represented by Chemical Formula 8 are shown below, but the present invention is not limited thereto. H (CH ₃ ) Si (OCH ₃ ) ₂ , HSi (OCH ₃ ) ₃ , (
CH ₃ ) ₃ SiOCH ₃ , Si (OCH ₃ ) ₄ , ClCH ₂ Si (OCH ₃
) ₃ , (ClCH ₂ CH ₂ O) ₂ Si (CH ₃ ) H,

(CH ₃ ) ₃ SiOCH ═CH ₂ , CH ₂ ═CHSi (O
CH ₃ ) ₃ , CH ≡ CCH ₂ OSi (CH ₃ ) ₃ , CF ₃ CH ₂ CH ₂ Si
_{(CH 3) (OCH 3)} 2, CH 2 = C (CH 3) OSi (CH 3) 3, Cl
CH ₂ (CH ₃ ) CHOSi (CH ₃ ) ₃ ,

(CH ₃ ) ₃ SiOCH ₂ CH ₂ CH ₃ , (CH ₃ ) _{3
SiOC (CH 3) 3, (} CH 3) 3 SiOCH (CH 3) CH 2 C
_{H 3, (CH 3) 3} SiO CH 2 CH (CH 3) 2, (CH 3) 3 SiO
_{(CH 2) 5 CH 3,} (CH 3) 3 SiOC (CH 3) 2 C ≡CH,

CH ₃ Si (OCH ₃ ) ₃ , (CH ₃ ) ₂ Si (OCH ₃ )
₂ , CH ₃ Si (OCH ₂ CH ₃ ) ₃ , (CH ₃ ) ₂ Si (OCH ₂ CH ₃ )
₂ , H (CH ₃ ) Si (OCH ₂ CH ₃ ) ₂ , (CH ₃ ) ₃ SiO CH ₂ CH
₃ , Si (OCH ₂ CH ₃ ) ₄ , and compounds represented by the following chemical formula 11.

[0021]

[Chemical 11]

In the method for producing an ester compound according to the present invention, a bond between a silicon atom and a carbon atom (≡Si—O) via an oxygen atom in a silane compound to an acyl fluoride group to be converted into an ester group. The ratio of —C≡) is at least equivalent, usually 1 to 5 mol / mol, preferably 1
It may be about 3 mol / mol. The reaction time is 3
The time may be 0 minutes to 2 hours, preferably 30 minutes to 1 hour. A solvent is not necessarily required in the method of the present invention, but an aprotic polar solvent such as toluene, hexane, tetrahydrofuran, or glymes, or a solvent such as a fluorine-based solvent, which does not affect the reaction of the present invention, may be used as necessary. You may use it.

[0023]

EFFECTS OF THE INVENTION According to the present invention, since hydrogen fluoride is not produced as a by-product in the manufacturing process, the method is safer and more workable than the conventional method, and the apparatus is not corroded. Is extremely excellent as

[0024]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. Example 1. 16.3 g of diethoxydimethylsilane was charged into a 100 ml three-necked flask equipped with a Dimroth, a thermometer, a dropping funnel and a stirrer, and while stirring, the acyl fluoride compound 4 represented by the following Chemical formula 12
9.8 g was added dropwise using a dropping funnel over 15 minutes.

[Chemical 12]

At the time of dropping, the internal temperature of the flask is 50 to
It heated using the oil bath so that it might become 60 degreeC. After completion of the dropping, the reaction was carried out at 60 ° C. for 1 hour with stirring, and then precision distillation was performed to obtain 32.5 g of a colorless and transparent fraction having a boiling point of 165 ° C./760 mmHg. The product was analyzed by ¹ H-NMR, ¹⁹ F
-As analyzed by NMR and IR,
It was confirmed that the compound was represented by Yield 62
%Met.

[Chemical 13]

¹ H-NMR (TMS standard) 1.21 ppm (-CH ₃ , t, 3H) 4.22 ppm (-CH _2- , q, 2H) ¹⁹ F-NMR (CF ₃ COOH standard) a: -3 .70 ppm b: −5.06 ppm c: −5.94 ppm d: −52.73 ppm e: −54.49 ppm f: −67.92 ppm

In the above, a to f represent the positions shown in the following Chemical formula 14.

Embedded image IR (see FIG. 1) ν _{c = o} : 1780 cm ⁻¹ ν _cF : 1100 to 1300 cm ⁻¹

Embodiment 2 FIG. To a 100 ml three-necked flask equipped with a Dimroth, a thermometer, a dropping funnel and a stirrer, 16.0 g of tetramethoxysilane was charged and stirred. Further, 49.8 g of the acyl fluoride compound represented by the following Chemical formula 15 was added dropwise using a dropping funnel over 15 minutes.

[Chemical 15]

At the time of dropping, the internal temperature of the flask is 50 to 50
It heated using the oil bath so that it might become 60 degreeC. After completion of the dropwise addition, the reaction was carried out at 60 ° C. for 1 hour with stirring, and then precision distillation was performed to obtain 37.7 g of a colorless and transparent fraction having a boiling point of 154 ° C./760 mmHg. The product was analyzed by ¹ H-NMR, ¹⁹ F
-As analyzed by NMR and IR,
It was confirmed that the compound was represented by Yield 74
%Met.

Embedded image

¹ H-NMR (TMS standard) 3.92 ppm (-CH ₃ , t, 3H) ¹⁹ F-NMR (CF ₃ COOH standard) a: -3.71 ppm b: -5.08 ppm c: -5. 90 ppm d: -52.74 ppm e: -54.40 ppm f: -67.92 ppm

In the above, a to f represent the positions shown in the following chemical formula 17.

[Chemical 17] IR (see FIG. 2) ν _{c = o} : 1785 cm ⁻¹ ν _cF : 1100 to 1300 cm ⁻¹

[Brief description of drawings]

1 is an IR spectrum of the ester compound obtained in Example 1. FIG.

2 is an IR spectrum of the ester compound obtained in Example 2. FIG.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinichi Sato 1 Hitomi, Otomi, Matsuida-cho, Usui-gun, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (3)

[Claims] 1. Reacting a compound having at least one acylfluoride group in a molecule with a silane compound having at least one bond between a silicon atom and a carbon atom via an oxygen atom in the molecule. A method for producing an ester compound, comprising: 2. A compound having an acylfluoride group in the molecule is represented by the general formula Rf ¹ (CO) F or F (CO) Rf.
^A method for producing the ester compound according to claim 1, which is represented by ² (CO) F; provided that Rf ¹ in the general formula is a monovalent perfluoroalkyl group or perfluoro having at least one ether bond. Alkyl ether group, Rf ²
Is a divalent perfluoroalkylene group or a perfluoroalkylene ether group having at least one ether bond. 3. A silane compound reacted with a compound having an acylfluoride group has a general formula R ¹ _n Si (OR ² ).
_2. An organosilane compound represented by _4-n.
Or a method for producing the ester compound described in 2;
R ¹ and R ² in the general formula are a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and n is an integer of 0 to 3.